Process for hydrogenation of 2,6,6-trimethyl cyclohexene derivatives, products produced thereby and organoleptic uses of said products

ABSTRACT

Described is a process for preparing hydrogenated derivatives of 2,6,6-trimethyl cyclohexene derivatives by means of treating said derivatives with hydrogen in the presence of a supported palladium catalyst such as palladium-on-calcium carbonate or palladium-on-barium sulfate in the presence of a quinoline activator. The resulting products are useful for their organoleptic properties as foodstuff flavorants and flavor enhancers, perfume composition ingredients, perfumed article ingredients and tobacco flavorants and flavor enhancers.

BACKGROUND OF THE INVENTION

The present invention provides butenoyl and butanoyl cyclohexane andcyclohexene compounds defined by the generic structure: ##STR1## whereinin the cyclohexyl group one of the dashed lines is a double bond and theother two dashed lines are single bonds or each of the three dashedlines are single bonds; in the butanoyl side chain, the dashed line is asingle bond or a double bond and wherein one of R₁ or R₂ is methyl andthe other of R₁ or R₂ is hydrogen. These compounds are prepared by astraightforward economical process also covered by this invention, whichprocess involves the treatment with hydrogen of a compound having thegeneric structure: ##STR2## wherein one of the dashed lines or both ofthe dashed lines are carbon-carbon double bonds and wherein one of R₁ orR₂ is hydrogen and the other of R₁ or R₂ is methyl. The compounds areprepared by means of the following reaction sequence: ##STR3## whereinthe cyclohexyl moiety of structure (II) contains a maximum of two doublebonds only when the cyclohexyl moiety of structure (I) contains twodouble bonds.

The present invention also provides for the utilization of the compoundsproduced by our invention and mixtures produced by the process of ourinvention which contain the compounds having the chemical structures:##STR4## or defined by the generic structure: ##STR5## wherein R₁, R₂and the dashed lines are as above defined, for their organolepticproperties in perfumes, perfumed articles, foodstuffs, foodstuffflavoring compositions, chewing gums, toothpastes, medicinal products,tobaccos, tobacco flavoring compositions, substitute tobaccos andsubstitute tobacco flavoring compositions.

In the perfumery art there is considerable need for constituents havingfloral, rose-like, sweet, dry fruity, tobacco-like aromas with heavyfruity (berry), hay-like and slightly camphoraceous undertones. Sweet,full ripe raspberry-like, fruity, grape juice-like, apple juice-like,dried-fruit-like damascenone-like, floral, woody, aroma and flavorcharacteristics are desirable in many fruit flavors, particularlyraspberry flavors, tangerine flavors, grape flavors and apply flavors.Wheat, fruity, hay-like, minty/spicey and woody aromas both prior to andon smoking in the mainstream and in the sidestream are desirable insmoking tobacco flavoring compositions and substitute smoking tobaccoflavoring compositions.

Specifically described herein are materials having such an organolepticprofile but which do not discolor with age. Such materials have a wideutilization in the presence of perfume compounds and in foodstuff flavorand tobacco flavoring compounds. A limited amount of such materials thatgive rise to one or more of these properties individually, is availablefrom natural sources but the natural materials are subject to widevariations in quality, are expensive and are often in critically shortsupply.

In addition, there is a continuing search for flavor compositions whichcan vary, fortify, modify, enhance, augment or otherwise improve theflavor and/or aroma of foodstuffs, medicinal products, toothpastes andchewing gums. To be satisfactory, such compositions should be stable,non-toxic and blendable with other ingredients to provide their ownunique flavor and aroma nuances without detracting from thecontributions of the co-ingredients. Preferably such compositions shouldbe naturally occurring or present in natural foodstuffs so that theiringestible safety can be readily recognized. These materials should becapable of being synthesized in a simple and economical manner. The needfor safe flavors in the berry fruit flavor area, especially theraspberry area, the grape flavor area and the apple flavor area is wellknown particularly in the fruit juice, ice cream and yogurt flavorareas. More specifically, there is a need for the development ofnon-toxic materials which can replace natural materials not readilyavailable having sweet, full ripe, raspberry--like, fruity, grapejuice-like, apple juice-like, driedfruit-like, floral and woody aromaand flavor characteristics.

The instant invention provides the foregoing which the prior art hasheretofore failed to provide. Furthermore, nothing in the prior artshows the unexpected, unobvious and advantageous value of carrying out ahydrogenation process on compounds having the generic structure:##STR6## wherein at least one of the dashed lines of structure (I) is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond and one of R₁ or R₂ is hydrogen and the otherof R₁ or R₂ is methyl, to provide compounds having the genericstructure: ##STR7## wherein at least two of the dashed lines in thecyclohexane moiety of structure II is a carbon-carbon single bond andthe other of the dashed lines in the cyclohexane moiety of structure IIis either a carbon-carbon single bond or a carbon-carbon bond; andwherein the dashed line in a butanoyl moiety of structure II is acarbon-carbon single bond or a carbon-carbon double bond and one of themoieties R₁ or R₂ is hydrogen and the other of the moieties R₁ or R₂ ismethyl.

Described in a prior art are mixtures presumed to be predominantlycis,trans-delta-damascone with minor amounts oftrans,trans-delta-damascone (Ayyar, Cookson and Kagi, J. Chem. Soc.,Perkin Trans. 1, 1975 (17) 1727-36 [title: "Synthesis of Delta-Damascone[trans-1-(2,6,6-trimethylcyclohex-3-enyl)but-2-en-lone] andBeta-Damascenone[trans-1-(2,6,6-trimethylcyclohexa-1,3-dienyl)but-2-en-1-one]"]. Thereaction sequence of the Ayyar synthesis, however, does not concern thestep of hydrogenation and is as follows: ##STR8## wherein the wavy lineis representative of a "cis" or "trans" configuration of the methylmoiety with respect to the acetyl or crotonoyl moiety, both of which arebonded to the cyclohexenyl moiety, the "cis" isomer presumably being themajor isomer and the "trans" isomer presumably being the minor isomer inthis reaction sequence.

In U.S. Pat. No. 3,956,392 at column 7 and 8 it is indicated thattrans,e-1-crotonyl-2,2,6-trimethylcyclohexane (totally saturated insofaras the ring moiety is concerned) has unexpected, unobvious propertiesover cis,e-1-crotonyl-2,2,6-trimethylcyclohexane; e-beta-damascenone ande-beta-damascone. The properties of the compound of U.S. Pat. No.3,956,392 are different in kind rather than degree from the organolepticproperties of the mixtures produced according to the hydrogenationprocesses of our invention.

Swiss Pat. No. 537,352 issued on July 13, 1973 discloses1(2-butenoyl)cyclohexenes having the structure: ##STR9## (wherein R maybe hydrogen) and this Swiss Patent is abstracted in Chem. Abstracts79:104808s.

The article, "Structure et synthese de la damascenone(trimethyl-2,6,6-trans-crotonoyl-1-cyclohexadiene-1,3), constituantodorant de l'essence de rose bulgare (Rosa damascena Mill.)" by E.Demole, P. Enggist, U. Sauberli and M. Stoll (referred to herein asDemole, et. al.) discloses the presence of2,6,6-trimethyl-1(trans-crotonyl)1,3-cyclohexadiene as an "odorousconstituent of Bulgarian rose oil". In addition, the Demole et. al.article discloses that dihydro-alpha-damascone results from the"catalytic hydrogenation" of "dehydro-alpha-damascone" produced via"dehydro-iso-ionol". On page 550 of the Demole article,1,5,5(trimethylbutyne-2-oyl)-6-cyclohexene is indicated to be treatedwith a Lindlar catalyst of the type used in the instant case therebyproducing a mixture containing 4:1 (mole ratio) of alpha-cis-damasconeand dihydro-alpha-damascone. The use of such Lindlar catalyst as is setforth in the Demole et. al. reference is well known in the art as isseen in Canadian Pat. No. 1,022,187 wherein citral,3,7-dimethyl-2,6-octadienal is converted to citronellal with yields inexcess of 95% by the use of a palladium catalyst and hydrogen gas in analkaline alcoholic reaction medium. It is indicated that the palladiumcan be used in any form in Canadian Pat. No. 1,022,187 but preferablythat the palladium is supported on a "suitable inert carrier such ascharcoal, alumina, barium carbonate, aluminum sulfate, carbon or silicagel".

Nothing in Canadian Pat. No. 1,022,187 or in the Demole et. al. articleimplied that the catalyst of the instant case can be used in such amanner in conjunction with the hydrogenation of compounds having thegeneric structure: ##STR10## wherein the dashed lines and R₁ and R₂ areas defined above, whereby compounds having the generic structure:##STR11## in admixture in the proportions indicated can be produced.

In addition, none of the foregoing references discloses the treatmentwith hydrogen of any one of the genus of compounds having the structure:##STR12## wherein at least one of the dashed lines is a carbon-carbondouble bond and the other of the dashed lines is a carbon-carbon singlebond and wherein one of R₁ or R₂ is hydrogen and the other of R₁ or R₂is methyl.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example I whereinthe peaks represent the indicated structures.

FIG. 2 is the mass spectrum for for peak 1 of the GLC profile of thereaction product produced according to Example I and is substantially1-butyryl-2,2,6-trimethylcyclohexane.

FIG. 3 is the infrared spectrum for peak 1 of the GLC profile of thereaction product produced according to Example I.

FIG. 4 is the NMR spectrum for peak 1 of the GLC profile of the reactionproduct produced according to Example I.

FIG. 5 is the mass spectrum for peak 2 of the GLC profile of thereaction product produced according to Example I which is substantially1-butyryl-2,2,6-trimethylcyclohex-5-ene.

FIG. 6 is the infrared spectrum for peak of the GLC profile of thereaction product produced according to Example I.

FIG. 7 is the NMR spectrum for peak 2 of the GLC profile of the reactionproduct produced according to Example I.

FIG. 8 is the mass spectrum for peak 3 of the GLC profile of thereaction product produced according to Example I, substantially1-butyryl-2,6,6-trimethylcyclohex-1-ene.

FIG. 9 is the infrared spectrum for peak 3 of the GLC profile of thereaction product produced according to Example I.

FIG. 10 is the NMR spectrum for peak 3 of the GLC profile of thereaction product produced according to Example I.

FIG. 11 is the GLC profile for the reaction product produced using apalladium-on-barium sulfate catalyst prepared according to the processof Example II(A). In this GLC profile the several peaks are indicated bystructures set forth on the drawing.

FIG. 12 is the mass spectrum for peak 1 of the GLC profile of thereaction product of Example II(A) which is essentially1-butyryl-2,6,6-trimethylcyclohex-2-ene.

FIG. 13 is the infrared spectrum for peak 1 of the GLC profile of thereaction product produced according to Example II(A).

FIG. 14 is the NMR spectrum for peak 1 of the GLC profile of thereaction product produced according to Example II(A).

FIG. 15 is the mass spectrum for peak 2 of the GLC profile of thereaction product produced according to Example II(A) which isessentially 1-butyryl-2,6,6-trimethylcyclohex-1-ene.

FIG. 16 is the infrared spectrum for peak 2 of the GLC profile of thereaction product of Example II(A).

FIG. 17 is the mass spectrum for peak 3 of the GLC profile of thereaction product produced according to Example II(A) which peak isessentially 1(2-butenoyl)-2,6,6-trimethylcyclohex-1-ene.

FIG. 18 is the infrared spectrum for peak 3 of the GLC profile of thereaction product of Example II(A).

FIG. 19 is the NMR spectrum of the product produced according to ExampleXVII.

THE INVENTION

The present invention provides an economical, efficient process forsynthesizing compounds having the generic structure: ##STR13## whereinin the cyclohexyl moiety of structure II, at least two of the dashedlines are carbon-carbon single bonds and the other of the dashed linesis either a carbon-carbon double bond or a carbon-carbon single bond;and wherein in the butanoyl side chain, the dashed line is either acarbon-carbon single bond or a carbon-carbon double bond; and whereinone of R₁ or R₂ is hydrogen and the other of R₁ or R₂ is methyl.Examples of structures of compounds represented by the genericstructure: ##STR14## The butanoyl trimethylcyclohexane derivatives ofour invention as well as mixtures thereof produced according to thehydrogenation process of our invention are capable of augmenting or orenhancing sweet, damascenone-like, full ripe raspberrylike, fruity,grape juice-like, apple juice-like, driedfruit-like and woody aromas andflavors particularly in raspberry- grape- tangerine- and apple-flavoredfoodstuffs.

The butenoyl and butanoyl cyclohexane and cyclohexene compounds andmixtures thereof of our invention are also capable of augmenting,enhancing or modifying the odor characteristics of perfume compositions,colognes and perfumed articles by imparting thereto or augmenting orenhancing the floral, rose-like, sweet, dried fruit, tobacco-likefragrance notes thus fulfilling a need in the field of perfumery.

In smoking tobacco and smoking tobacco flavoring compositions and insubstitute smoking tobacco and in substitute smoking tobacco flavoringcompositions the compounds produced according to the novel process ofour invention, the butenoyl and/or butanoyl cyclohexane and cyclohexenecompounds augment and enhance the sweet, fruity, hay-like, minty/spicey,hay-tobacco-like, haytea-like aroma and taste notes prior to and onsmoking in the mainstream and in the sidestream.

The butenoyl and/or butanoyl cyclohexane and cyclohexene compounds andmixtures thereof of our invention are produced by, in general, reactingwith hydrogen a compound or mixture of compounds defined according tothe structure: ##STR15## where at least one of the dashed lines in thecyclohexane moiety of structure I is a carbon-carbon double bond and theother of the dashed lines is a carbon-carbon single bond and one of R₁or R₂ is hydrogen and the other of R₁ or R₂ is methyl according to thefollowing reaction scheme: More specifically, when carbon-carbon doublebonds exist at the "1" and "3" positions of compound I, hydrogenation ofcompound I in the presence of a supported palladium catalyst(palladium-on-calcium carbonate or palladium-onbarium sulfate) and asolvent such as ethyl acetate will give rise to a mixture of compoundscontaining a compound having unsaturation at the Δ²,3 position orcomplete saturation in the ring moiety. It is preferable to also includea catalyst "deactivator" with the supported palladium catalyst such asquinoline. In addition, compounds in the resulting mixtures will beproduced wherein there is a saturation at the Δ²,3 position of the sidechain or there is unsaturation at that position. Even more specifically,when a palladium-on-calcium carbonate catalyst is used in thehydrogenation of a compound having the structure: ##STR16## thefollowing reaction takes place: ##STR17##

On the other hand, when the compound reacted is, for example,cis,trans-delta-damascone (as described and synthesized by Ayyar, et.al. cited supra) the reaction sequence taking place is as follows:##STR18##

When the catalyst used is palladium supported on barium sulfate, and theresultant has the structure: ##STR19##

the reaction taking place is as follows: ##STR20##

The amount of palladium in the catalyst composition may vary from 2% upto about 10% with the support being either calcium carbonate or bariumsulfate. The preferable quantity of palladium in the catalyst is about5%. The ratio of catalyst (including the support) to reactant having thegeneric structure: ##STR21## for example, compounds such as betadamascenone having the structure: ##STR22## may vary from 0.05:1 up to0.5:1 with a preferred ratio of catalyst:reactant being about 0.1:1(weight:weight). When using a palladium-on-calcium carbonate catalyst,it is preferred that a solvent also be used in the reaction withhydrogen and such solvent is preferably an inert solvent such as aninert ester, for example, ethyl acetate or n-propyl acetate or n-butylacetate or ethyl n-propionate or n-propyl-n-propionate or n-butyln-propionate or diethyl phthalate. The concentration of reactant such asbeta damascenone in solvent may vary from about 1:10 up to about 1:50with a concentration of reactant in solvent of about 5% beingpreferable.

The hydrogenation reaction preferably takes place at "ambient"conditions, i.e., room temperature, 20°-30° C. and one atmospherepressure. However, higher pressures up to about 100 atmospheres andhigher temperatures up to about 50° C. may be used without detrimentallyaffecting the yield of desirable product produced. Indeed, in manyinstances higher temperatures of reaction give rise to shorter times ofreaction and use of shorter times of reaction is advantageous from aneconomical standpoint.

Examples of the products produced according to the process of ourinvention and their organoleptic properties are as follows:

                                      TABLE I                                     __________________________________________________________________________    Structure of Products                                                         either taken alone                                                                        Perfumery    Food Flavor   Tobacco Flavor                         or in admixture                                                                           Properties   Affecting Properties                                                                        Affecting Propoerties                  __________________________________________________________________________     ##STR23##  At 1% in dipropylene gly- col, a sweet, dry, fruity, floral                   aroma with hay tobacco nuances.                                                            A sweet, damascenone-like, full, ripe,                                        raspberry-like, aroma and flavor character at 1                               ppm.          A fruity, berry-like, damascenone-l                                           ike, hay tea-like aroma with                                                  sweet, floral, fruity nuances                                                 prior to and on smoking in the                                                mainstream and the sidestream and                                             also resulting from treatment of                                              the filter (20 micro- liter filter                                            or 200 ppm.).                           ##STR24##               A sweet, fruity, raspberry- like, grape                                       juice-like, apple juice-like, dried- fruit-like,                              damascenone aroma and flavor character- istics                                with a cooling effect at 1 ppm.                       ##STR25##  A floral (rose) fruity (prune, berry-like) aroma.                                          A damascenone-like, floral woody and fruity                                   aroma and flavor characteristics 2.0 ppm.             ##STR26##  A burnt, rosey aroma with weak floral nuances.                                             A fruity, woody, floral damascenone-like aroma                                and flavor characteristics at 2 ppm.                  ##STR27##  A floral, rose-like aroma with heavy fruity                                   (berry) undertones; also hay and slightly camphoraceous                       nuances.     A sweet, fruity, rasp- berry-like, rosebuds-                                  like aroma with sweet, fruity, raspberry flavor                               characteristics with a rosebuds nuance  at 0.005                              ppm.          A sweet, fruity, hay minty/spicey,                                            woody, aroma and flavor profile                                               both prior to and on smoking in                                               the mainstream and in the                                                     sidestream.                             ##STR28##                                                                     ##STR29##                                                                     ##STR30##                                                                     ##STR31##                                                                    __________________________________________________________________________

When the butenoyl and butanoyl cyclohexane and cyclohexene compounds andmixtures thereof of our invention are used as food flavor adjuvants, thenature of the co-ingredients included with the butenoyl and butanoylcyclohexane and cyclohexene compounds and mixtures thereof of ourinvention used in formulating the product composition will also serve toalter, modify, augment or enhance the organoleptic characteristics ofthe ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste.

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschickle, or substitutes therefor, including jelutong, guttakay rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates the butenoyl and butanoyl cyclohexane and cyclohexenecompounds and mixtures thereof of our invention, and in addition,sweetening agents which may be sugars, including sucrose or dextroseand/or artificial sweeteners such as cyclamates or saccharin. Otheroptional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and/or taste nuances. Such materialsmay in general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavordispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid and cis and trans 2-methyl-3-pentenoic acids;ketones and aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetylmethyl carbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal, beta, beta-dimethyl-acrolein, methyl-n-amyl ketone, 2-hexanal,2-hexenal, iso-pentanal, hydrocinnamic aldehyde cis-3-hexenal,2-heptenal, n-nonyl aldehyde, 4-(p-hydroxyphenyl)-2-butanone,alpha-ionone, beta-ionone, methyl-3-butanone, benzaldehyde,beta-damascone, beta-damascenone, acetophenone, 2-heptanone,o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone,2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 5-methyl furfural, cinnamaldehyde,beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyl diphenyl, methylnaphthalene, mycrene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethyl naphthalene, undecane, caryophyllene,1-phellandrene, p-cymene, 1-alphapinene; pyrazines such as2,3-dimethylpyrazine, 2-5-dimethylpyrazine, 2-6-dimethylpryazine,3-ethyl-2,5-dimethyl-pryazine, 2-ethyl-3,5,6-trimethylpryazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones such as delta nonalactone, gamma nonalactone, deltadodecalactone, gamma dodecalactone, sulfides, e.g., methyl sulfide andother materials such as maltol, acetoin and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the butenoyl and butanoylcyclohexane and cyclohexene compounds and mixtures thereof of ourinvention by not covering or spoiling the organoleptic properties (aromaand/or taste) thereof; (ii) be non-reactive with the butenoyl andbutanoyl cyclohexane and cyclohexene compounds and mixtures thereof ofour invention and (iii) be capable of providing an environment in whichthe butenoyl and butanoyl cyclohexane and cyclohexene compounds andmixtures thereof of our invention can be dispersed or admixed to providea homogeneous medium. In addition, selected of one or more flavoringadjuvants, as well as the quantities thereof will depend upon theprecise organoleptic character desired in the finished product. Thus, inthe case of flavoring compositions, ingredient selection will vary inaccordance with the foodstuff, chewing gum, medicinal product ortoothpaste to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount of thebutenoyl and/or butanoyl cyclohexane and cyclohexene compounds and/ormixtures thereof of our invention employed in a particular instance canvary over a relatively wide range, depending upon the desiredorganoleptic effects to be achieved. Thus, correspondingly, greateramounts would be necessary in those instances wherein the ultimate foodcomposition to be flavored is relatively bland to the taste, whereasrelatively minor quantities may suffice for purposes of enhancing thecomposition merely deficient in natural flavor or aroma. The primaryrequirement is that the amount selected to be effective, i.e.,sufficient to alter, modify or enhance the organoleptic characteristicsof the parent composition, whether foodstuff per se, chewing gum per se,medicinal product per se, toothpaste per se, or flavoring composition.

The use of insufficient quantities of butenoyl and/or butanoylcyclohexane and cyclohexene compounds and/or mixtures thereof will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities provide needlessly costly and in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of butenoyl and butanoylcyclohexane and cyclohexene compounds and mixtures thereof ranging froma small but effective amount, e.g., 0.002 ppm up to about 100 ppm basedon total composition are suitable. Concentrations in excess of themaximum quantity stated are not normally recommended, since they fail toprovide commensurate enhancement of organoleptic properties. In thoseinstances, wherein the butenoyl and butanoyl cyclohexane and cyclohexenecompounds and mixtures thereof of our invention are added to thefoodstuff as an integral component of a flavoring composition, it is, ofcourse, essential that the total quantity of flavoring compositionemployed by sufficient to yield an effective concentration of butenoyland/or butanoyl cyclohexane and cyclohexene compounds or mixturesthereof in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the butenoyl and/or butanoyl cyclohexaneand cyclohexene compounds or mixtures thereof of our invention inconcentrations ranging from about 0.1% up to about 15% by weight basedon the total weight of the said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the butenoyl and/or butanoyl cyclohexaneand cyclohexene compounds or mixtures thereof of our invention with, forexample, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticulate solid product. Pre-prepared flavor mixes in powder form,e.g., fruit-flavored powder mixes are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and the butenoyl and/orbutanoyl cyclohexane and cyclohexene compounds or mixtures thereof ofour invention in a dry blender until the requisite degree of uniformityis achieved.

It is presently preferred to combine with the butenoyl and/or butanoylcyclohexane and cyclohexene compounds or mixtures thereof of ourinvention, the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl Anthranilate;

5-Methyl furfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,2-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

Beta-Damascone (1-crotonyl-2,6,6-trimethyl-cyclohex-1-ene);

Beta-Damascenone (1-crotonyl-2,6,6-trimethyl-cyclohexa-1,3-diene);

Beta-cyclohomocitral (2,6,6-trimethylcyclohex-1-ene carboxaldehyde);

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxybenzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene); and

2-(4-Hydroxy-4-methylpentyl) norbornadiene.

The butenoyl and/or butanoyl cyclohexane and cyclohexene compounds ormixtures thereof and one or more auxiliary perfume ingredients,including, for example, alcohols, aldehydes, ketones other than thebutenoyl and/or butanoyl cyclohexane and cyclohexene compounds ormixtures thereof of our invention, terpinic hydrocarbons, nitriles,esters, lactones, natural essential oils and synthetic essential oils,may be admixed so that the combined odors of the individual componentsproduce a pleasant and desired fragrance, particularly and preferably inrose fragrances. Such perfume compositions usually contain (a) the mainnote or the "bouquet" or foundation stone of the composition; (b)modifiers which round off and accompany the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, the butenoyland/or butanoyl cyclohexane and cyclohexene compounds or mixturesthereof of our invention can be used to alter, modify or enhance thearoma characteristics of a perfume composition, for example, byutilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of butenoyl and/or butanoyl cyclohexane and cyclohexenecompounds or mixtures thereof of our invention which will be effectivein perfume compositions as well as in perfumed articles and colognesdepends on many factors, including the other ingredients, their amountsand the effects which are desired. It has been found that perfumecompositions containing as little at 0.01% of the butenoyl and/orbutanoyl cyclohexane and cyclohexene compounds (or mixtures thereof) oreven less (e.g., 0.005%) can be used to impart a sweet, fruity, floral,rosey aroma with hay-tobacco undertones to soaps, anionic, cationic andnonionic detergents, fabric softener articles (such as BOUNCE®, aregistered trademark of the Procter & Gamble Company of Cincinnatti,Ohio), cosmetics or other products. The amount employed can range up to70% of the fragrance components and will depend on considerations ofcost, nature of the end product, the effect desired on the finishedproduct and the particular fragrance sought.

The butenoyl and/or butanoyl cyclohexane and cyclohexene compounds ormixtures thereof of our invention are useful (taken alone or togetherwith other ingredients in perfume compositions) as (an) olfactorycomponent(s) in solid and liquid anionic, cationic and nonionicdetergents and soaps, space odorants and deodorants, perfumes, colognes,toilet water, bath preparations, such as creams, deodorants, handlotions and sunscreens; powders, such as talcs, dusting powders, facepowders and the like. When used as olfactory components as little as0.1% of the butenoyl and/or butanoyl cyclohexane and cyclohexenecompounds or mixtures thereof of our invention will suffice to impart anintense floral note to rose formulations. Generally, no more than 5% ofthe butenoyl and/or butanoyl cyclohexane and cyclohexene compounds ormixtures thereof of our invention, based on the ultimate end product, isrequired in the perfume composition.

In addition, the perfume compositions or fragrance compositions of ourinvention can contain a vehicle, or carrier for the butenoyl and/orbutanoyl cyclohexane and cyclohexene compounds or mixtures thereof ofour invention. The vehicle can be a liquid such as an alcohol, anon-toxic alcohol, a non-toxic glycol, or the like. The carrier can alsobe an absorbent solid, such as a gum (e.g., gum arabic) or componentsfor encapsulating the composition (such as gelatin), for example, bymeans of coacervation.

It will thus be apparent that the butenoyl and/or butanoyl cyclohexaneand cyclohexene compounds or mixtures thereof of our invention can beutilized to alter, modify or enhance sensory properties, particularlyorganoleptic properties, such as flavor(s) and/or fragrance(s) of a widevariety of consumable materials.

Furthermore, the butenoyl and butanoyl cyclohexane and cyclohexenecompounds of our invention are capable of supplying and/or potentialtingcertain flavor and aroma notes usually lacking in many tobacco flavorsheretofore provided.

As used herein in regard to tobacco flavors, the terms "alter" and"modify" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland tobacco, tobacco substitutes, ortobacco flavor formulations or augmenting the existing flavorcharacteristic where a natural flavor is deficient in some regard orsupplementing the existing flavor impression to modify its quality,character or taste".

As used herein, the term "enhance" is intended to mean theintensification (without change in kind of quality of aroma or taste) ofone or more taste and/or aroma nuances present in the organolepticimpression of a tobacco or a tobacco substitute or a tobacco flavor.

Our invention thus provides an organoleptically improved smoking tobaccoproduct and additives therefor, as well as methods of making the samewhich overcome specific problems heretofore encountered in whichspecific desired floral, musty, hay- tea-like, sweet and fruity aromaand taste nuances are created or enhanced and may be readily controlledand maintained at the desired uniform level regardless of variations inthe smoking tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various sweet, fruity, hay-like, minty/spicey,fruity/berry-like, damascenone-like and hay tea-like notes may beimparted to smoking tobacco products and may be readily varied andcontrolled to produce the desired uniform flavor characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient at leastone of the butenoyl and/or butanoyl cyclohexane and cyclohexenecompounds or mixtures thereof of our invention.

In addition to the butenoyl and butanoyl cyclohexane and cyclohexenecompounds and mixtures thereof of our invention, other flavoring andaroma additives may be added to the smoking tobacco materials orsubstitute therefor either separately or in admixture with the butenoyland/or butanoyl cyclohexane and cyclohexene compounds or mixturesthereof of our invention as follows:

(i) Synthetic Materials:

Beta-ethyl-cinnamaldehyde;

Beta-cyclohomocitral;

Eugenol;

Dipentene;

Beta-damascenone;

Alpha-damascone;

Beta-damascone;

Cis,trans-alpha-damascone;

Maltol;

Ethyl Maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1,b]-furan;

4-Hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. 3,589,372issued on June 29, 1971.

(ii) Natural Oils:

Celery seed Oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg Oil;

Origanum Oil.

An aroma and flavoring concentrate containing one or more of thebutenoyl and/or butanoyl cyclohexane and cyclohexene compounds ormixtures thereof of our invention, and, if desired, one or more of theabove-indicated additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapper.The smoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of natural and/or sweet notes,we have found that satisfactory results are obtained if the proportionby weight of the sum total of the butenoyl and/or butanoyl cyclohexaneand cyclohexene compounds (or mixtures thereof) to smoking tobaccomaterial is between 250 ppm. and 1,500 ppm. (0.025-0.15%) of the activeingredients to the smoking tobacco material. We have further found thatsatisfactory results are obtained if the proportion by weight of the sumtotal of the butenoyl and/or butanoyl cyclohexane and cyclohexenecompounds (or mixtures thereof) used to flavoring material is between2,500 and 15,000 ppm. (0.25%-1.5%).

Any convenient method for incorporating the butenoyl and/or butanoylcyclohexane and cyclohexene compounds (or mixtures there) in the smokingtobacco product may be employed. Thus, the butenoyl and/or butanoylcyclohexane and cyclohexene compounds or mixtures thereof of ourinvention taken alone or taken further together with other flavoringadditives as set forth above, may be applied by means of a suitableapplicator such as a brush or roller on the paper or leaf wrapper forthe smoking product, or it may be applied to the filter by eitherspraying, dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the butenoyl and/orbutanoyl cyclohexane and cyclohexene compounds (or mixtures thereof) ofour invention in excess of the amounts or concentrations above-indicatedso that when blended with other tobaccos, the final product will havethe percentage within the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution of the 1-(2,6,6-trimethyl-2-cyclohexene-1-oyl)-1-butanoneproduced according to Example II, infra, in an amount to provide atobacco composition containing 200 ppm. by weight of said1-(2,6,6-trimethyl-2-cyclohexene-1-oyl)-1-butanone on a dry basis.

Thereafter, the alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by means of the usual techniques. Thecigarette when treated as indicated has a desired and pleasing aroma(increased smoke body sensation in the mouth with enhanced tobacco-likenotes and pleasant aromatic nuances) which is detectable in the main andsidestreams when the cigarette is smoked. This aroma is described ashaving a fruity, berry-like, damascenone-like, hay-tea-like aroma withsweet, floral and fruity undertones prior to and on smoking both in themainstream and the sidestream.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise, the butenoyl and/or butanoyl cyclohexane andcyclohexene compounds or mixtures thereof of our invention can beincorporated with materials such as filter tip materials, seam paste,packaging materials and the like which are used along with smokingtobacco to form a product adapted for smoking. Furthermore, the butenoyland/or butanoyl cyclohexane and cyclohexene compounds or mixturesthereof can be added to certain smoking tobacco substitutes of naturalor synthetic origin (e.g., dried lettuce leaves) and, accordingly, bythe term "tobacco" as used throughout this specification is meant anycomposition intended for human consumption by smoking, whether composedof tobacco plant parts or substitute materials or both.

The following Examples serve to illustrate our invention. However, ourinvention is not intended to be limited thereto but is only intended tobe limited insofar as the Claims are concerned. All parts andpercentages given herein are by weight unless otherwise specified.

EXAMPLE I PREPARATION OF MIXTURE OF HYDROGENATED DERIVATIVES OF BETADAMASCENONE ##STR32## One gram of beta damascenone having the structure:##STR33## is added to a 50 ml. reaction flask equipped with stirrer,thermometer, gas addition tube along with 20 ml. of ethyl acetate and100 mg. of "Lindlar" catalyst which is a mixture of 5%palladium-on-calcium carbonate. The resulting mixture is stirred whileadding hydrogen at 20°-25° C. and one atmosphere pressure until 120 ml.of hydrogen is absorbed. Preparative GLC (conditions: 10 ft.×1/8 in. 5%carbowax 20 M column programmed at 100°-220° C. at 4° C. per minute)followed by nuclear magnetic resonance analysis, infrared analysis andmass spectral analysis yields the information that the mixture contains20% of the compound having the structure: ##STR34## 14.7% of thecompound having the structure: ##STR35## and 59.4% of the compoundhaving the structure: ##STR36##

The mass spectral analysis for peak 1 of the GLC profile, the compoundhaving the structure: ##STR37## is set forth in FIG. 2. The GLC profileis set forth in FIG. 1. The infrared spectrum for peak 1 is set forth inFIG. 3. The NMR spectrum for peak 1 is set forth in FIG. 4.

Peak 2 is substantially the compound having the structure: ##STR38## Themass spectrum is set forth in FIG. 5. The infrared spectrum for peak 2is set forth in FIG. 6. The NMR spectrum for peak 2 is set forth in FIG.7.

Peak 3 is essentially a compound having the structure: ##STR39## Themass spectrum for peak 3 is set forth in FIG. 8. The infrared spectrumfor peak 3 is set forth in FIG. 9. The NMR spectrum is set forth in FIG.10.

The same experiment as set forth above is carried out wherein 1/2 gramof beta damascenone is reduced at 20°-25° C. and 1 atmosphere pressureover 100 mg. of Lindlar catalyst in 10 ml. ethyl acetate. 130 ml. ofhydrogen are absorbed. The product is then analyzed. The componentsformed according to GLC mass spectral NMR and IR analyses are asfollows:

Peak 1 having the structure: ##STR40## Peak 2 having the structure:##STR41## Peak 3 having the structure: ##STR42##

EXAMPLE II ##STR43## EXAMPLE II(a)

To a 250 ml. reaction flask is added 10 grams of beta damascenone havingthe structure: ##STR44##

100 ml. ethyl acetate and 0.25 grams of 5% palladium-on-barium sulfateand 0.25 grams of quinoline are then added. The mixture is thenhydrogenated at atmospheric pressure and a temperature of 20°-25° C.until an uptake of 1,415 ml. of hydrogen is indicated. GLC analyses arerun at about every 100 ml. of hydrogen uptake. The reaction is caused tocease when no more beta damascenone is present. The catalysts are thenfiltered off and the ethyl acetate evaporated leaving 9.9 grams perproduct. 150 ml. anhydrous diethyl ether is added and the solution ofcrude product is washed twice with a 4% aqueous hydrochloric acidsolution (20 ml.) and twice with a saturated sodium chloride solution(30 ml.). The ether solution is then dried over anhydrous magnesiumsulfate and evaporated leaving 10.0 grams of recovered material. Thismaterial is then distilled on a Naster-Faust spinning band columnyielding the following fractions:

    ______________________________________                                               Vapor                                                                  Fraction                                                                             Temp.   Liquid   Vacuum Reflux Weight of                               No.    (°C.)                                                                          Temp.    mm. Hg Ratio  Fraction(gm)                            ______________________________________                                        1      37-44   113-115  .25-.25                                                                              100:1  0.20                                    2      45      119      0.25   100:1  0.40                                    3      43      120      0.25   100:1  0.30                                    4      80      121      0.25   100:1  0.30                                    5      70      119      0.4    100:1  0.05                                    6      70      118      0.4    100:1  0.10                                    7      60-55   122-127  .3-.3  50:1   0.10                                    8      57      132      0.45   50:1   0.20                                    9      64      134      0.45   50:1   0.60                                    10     68      136      0.45   50:1   0.80                                    11     66      134      0.50   50:1   0.70                                    12     62      135      0.45   50:1   0.30                                    13     66      143      0.60   200:1  0.50                                    14     70      145      0.60   200:1  0.30                                    15     70      147      0.50   200:1  0.60                                    16     64      150      0.50   200:1  0.40                                    17     43-52   170-180  .15-.15                                                                              100:1  0.40                                    18     51      195      0.15   100:1  0.20                                    19     55      205      0.10   100:1  0.20                                    20     53      210      0.10   100:1  0.10                                    21     71      235      .125   100:1  0.20                                    22     71      235      .125   100:1  0.05                                    23     41-42   27-28    0.4-0.4                                                                              100:1  0.05                                    24     42      280      .4     5:1    0.15                                                                          7.2                                     ______________________________________                                    

Fractions 2 and 3 are primarily compound having the structure: ##STR45##

Fractions 7 and 8 are primarily compounds having the structure:##STR46##

Fractions 12-24 are primarily compounds having the structure: ##STR47##

FIG. 11 is the GLC profile for the reaction product.

FIG. 12 is the mass spectrum for peak 1 of the reaction product which issubstantially compound having the structure: ##STR48##

FIG. 13 is the infrared spectrum for peak 1 of this example.

FIG. 14 is the NMR spectrum for peak 1 of this example.

FIG. 15 is the mass spectrum for peak 2 the GLC profile which issubstantially compound having the structure: ##STR49##

FIG. 16 is the infrared spectrum for peak 2.

FIG. 17 is the mass spectrum for peak 3 of the GLC profile of thereaction product of this example which is compound having the structure:##STR50##

FIG. 18 is the infrared spectrum for peak 3.

EXAMPLE II(b)

To a 25 ml reaction flask equipped with thermometer, hydrogen additionline and magnetic stirrer is added 0.5 grams of damascenone having thestructure: ##STR51## 25 mg of palladium-on-barium sulfate (5% palladium)and 10 ml of ethyl acetate. The mixture is stirred and 0.25 mg ofquinoline is added. The mixture is reduced with hydrogen (at 29°-30° C.and 1 atmosphere pressure) until an uptake of 130 ml is accomplished.During reduction the molecular weight of damascenone is monitored untilthe complete disappearance thereof. On analysis 16% by weight of acompound having the structure: ##STR52## and 40% of the compound havingthe structure: ##STR53## is produced. The quinoline is removed by meansof washing with 10% aqueous hydrochloric acid followed by neutralizationwith a saturate sodium chloride solution (three 20 ml washed). Theresulting mass is then dried over anhydrous magnesium sulfate and theether is removed yielding 0.4 grams.

EXAMPLE II(c)

A system for carrying out hydrogenation is set up with a 1,000 cc flaskequipped with thermometer, septum for purging and taking of samples, ahydrogen source and a biuret for measurement of hydrogen uptake. Theflask contains a magnetic stirring bar.

The reaction flask is charged with beta damascenone (50 grams; 0.26moles) 1.25 grams of a 5% palladium-on-barium sulfate catalyst; 500 mlethyl acetate and 1.25 grams of quinoline.

The hydrogen is added slowly 100 cc at a time and monitored by means ofGLC analysis, while maintaining the temperature at 25° C. at a pressureof one atmosphere.

A total of 5,566 ml hydrogen is used. The final GLC analysis indicatesthe presence of isomers having the following structures: ##STR54##

The reaction mass is filtered whereby the catalyst is gravity filteredout. The catalyst is washed several times with ethyl acetate and theethyl acetate washing are added to the supernatant liquid.

The reaction mass is then passed through a column packed with silica gelto remove any extra catalyst.

The reaction mass is then washed with two 100 ml portions of 4% aqueoushydrochloric acid in order to wash out the quinoline. The reaction massis then washed with four 50 ml portions of saturated sodium chloride.The reaction mass is then dried using anhydrous magnesium sulfate andfiltered.

The reaction mass is then placed in a 500 ml receiver and a solvent isevaporated on a rotary evaporator yielding 53.5 grams of product. Theproduct is then rushed over in a rotary evaporator yielding 53.5 gramsof product. The product is then rushed over in a microdistillation setupyielding the following fractions:

    ______________________________________                                               Vapor                          Weight of                               Fraction                                                                             Temp.    Liquid  Vacuum Reflux Fraction                                No.    (°C.)                                                                           Temp.   mm. Hg.                                                                              Ratio  (grams)                                 ______________________________________                                        1      75/76    83/85   .25/.25                                                                              1:00/1:05                                                                            1.2                                     2      77       86      .25    1:15   1.3                                     3      80       86      .25    1:18   1.8                                     4      50       101     .25    1:22   .7                                      5      88       91      .25    1:45   1.3                                     6      112      110     .15    2:40   1.8                                     7      72       96      0.135  3:05   1.9                                     8      82       97      0.133  3:11   8.9                                     9      86       99      0.133  3:16   9.3                                     10     86       105     .133   3:27   10.3                                    11     79       128     .133   3:35   7.5                                     12     62       205     0.125  17:45  0.6                                                                           46.6                                    ______________________________________                                    

EXAMPLE III OTTO OF ROSE PERFUME FORMULATION

The following mixture is prepared:

    ______________________________________                                        Ingredients              Parts by Weight                                      ______________________________________                                        Phenyl acetic acid       5                                                    Hydroxycitronellal       10                                                   Geraniol                 125                                                  Citronellol              150                                                  Phenyl ethyl alcohol     50                                                   Phenyl ethyl acetate     4                                                    Ethyl phenyl acetate     5                                                    Citronellyl formate      20                                                   Geranyl acetate          25                                                   Linalool                 15                                                   Terpineol                10                                                   Eugenol                  3                                                    Phenyl acetaldehyde dimethyl acetal                                                                    5                                                    Benzyl acetate           3                                                    Guaiacwood Oil           5                                                    3-methylthio-4-heptanone produced according                                   to the process of Part "C" of Example I of                                    U.S. Pat. No. 4,065,408 issued on 12/27/77                                    Bulked fractions 8-11 of the mixture of com-                                  pounds having the structures of the product                                   produced according to Example I:                                                                       5                                                    ______________________________________                                         ##STR55##                                                                     ##STR56##                                                                     ##STR57##                                                                     ##STR58##                                                                    ______________________________________                                    

The hydrogenated beta damascenone mixture produced according to ExampleI used herein imparts to this Otto of Rose formulation floral androse-like notes with heavy fruity (berry) nuances and in addition hayand slightly camphoraceous topnotes.

The use of the 3-methylthio-4-heptanone herein imparts a green, fruity,spicey topnote to this Otto of Rose perfume formulation. The combinationof the 3-methylthio-4-heptanone together with the product producedaccording to Example I (bulked fractions 8-11 inclusive) causes the Ottoof Rose perfume formulation to be much more "natural like".

When the mixture of Example I is replaced by the mixture of ExampleII(a), (b) or (c), the Otto of Rose perfume formulation is an "naturallike" and has the same aroma nuances, topnotes and undertones as doesthe formulation containing the hydrogenation product of beta damascenoneproduced according to Example I.

EXAMPLE IV

PREPARATION OF A SOAP COMPOSITION

Chips of soap comprising 17% coconut fatty acid soap and 83%hydrogenated tallow acids sodium soap are mixed with titanium dioxide (awhite pigment), preservative, the perfume composition of Example III anda bacteriostat in the proportions given below:

    ______________________________________                                        Ingredient              Percent                                               ______________________________________                                        17:83 coco:tallow sodium soap chips                                                                   95:85                                                 Titanium dioxide        0.50                                                  Preservative            0.15                                                  Perfume composition prepared according                                        to Example III          1.50                                                  Bacteriostat            1.00                                                  ______________________________________                                    

The soap chips, white pigment, preservative, perfume compositionprepared according to Example III and bacteriostat are mixed and milled.The milled chips are fed into the top worn of a 4" double-barrel vacuumplodder.

After the segments pass through the die plate as described in thedrawings of United Kingdom Pat. No. 1,494,278, a 10% aqueous dispersionof a blue pigment (Monastral Green GWD available from E. I. duPontdeNemours, U.S.A. "Monastral" is a registered trademark) is sprayed ontothe segments at a predetermined rate of about half a pound of pigmentdispersion per 100 pounds of soap.

The die plate used has circular holes each having a diameter of 1.25inches and is more particularly described in Example I of United KingdomPat. No. 1,494,278. The knife has found blades and is rotated at asufficient speed to produce segments 2 inches long. The geometric ratiois 5. The final soap bar has a distinct marbled appearance with anundiluted white background, bright blue colored areas and a cleardemarcation between the white and blue areas. The resulting soap alsohas an excellent Otto of Rose-type aroma with distinct floral and heavyfruity undertones and hay and slightly camphoraceous topnotes.

EXAMPLE V PREPARATION OF A SOAP COMPOSITION

100 grams of soap chips prepared according to Example IV but without anyperfume added, is mixed with 1 gram of the bulked fractions 8-11 of thehydrogenated beta damascenone mixture produced according to Example Iuntil a substantially homogeneous composition is obtained. The perfumedheterogeneous mixture is then heated to a temperature of 150° C. andmaintained at that temperature for a period of 20 minutes. The mixtureis then molded into a soap bar and permitted to cool to roomtemperature. The resulting soap bar has an excellent floral, rose-likearoma with heavy fruity (berry) nuances and hay and slightlycamphoraceous topnotes.

When the mixture of Example I is replaced by the mixture preparedaccording to Examples II (a), (b) or (c) or when the mixture of ExampleI is replaced by the compound having the structure: ##STR59## theresulting soap has very similar aromas to that produced when using thebulked fractions 8-11 prepared according to Example I. However, thecompound having the structure: ##STR60## also imparts sweet, dry, fruityaroma nuances with hay tobacco undertones in addition to the aromanuances set forth above.

EXAMPLE VI PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (a nonionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Pat. No. 985,190 issued on Mar. 9, 1976) is mixed with 0.10,0.15, 0.20, 0.25, or 0.30 grams of the mixture of hydrogenatedderivatives of beta damascenone prepared according to Example I (bulkedfractions 8-11) until a substantially homogeneous composition isobtained. The composition has an excellent floral, rose-like aroma witha heavy fruity (berry) undertone and hay and slightly camphoraceoustopnotes.

When this mixture (bulked fractions 8-11 of Example I) is replaced bythe compound having the structure: ##STR61## the resulting detergent hasan excellent sweet, dry, fruity, floral aroma with hay tobacco nuances.When this compound is replaced by the "beta isomer" having thestructure: ##STR62## a sweeter, more tobacco aroma is produced in thedetergent with deeper floral nuances.

EXAMPLE VII

A total of 100 grams of a detergent powder (a nonionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Pat. No. 985,190 issued on Mar. 9, 1976) is mixed with 0.10,0.15, 0.20, 0.25, or 0.30 grams of the perfume composition preparedaccording to Example III until a substantially homogeneous compositionis obtained. This composition has an excellent Otto of Rose aroma withfloral, heavy fruity nuances and hay and slightly camphoraceoustopnotes.

EXAMPLE VIII PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents with rich, pleasant Otto of Rose aromasare prepared containing 0.10%, 0.15%, 0.20%, 0.25% or 0.30% of themixture prepared according to Example III. They are prepared by addingand homogeneously admixing the appropriate quantity of the compositionof Example III in the liquid detergent. The liquid detergents are allproduced using anionic detergents containing a 50:50 mixture of sodiumlauroyl sarcosinate and potassium N-methyl lauroyl tauride. Thedetergents all possess a pleasant Otto of Rose fragrance with floral andheavy fruity undertones and hay and slightly camphoraceous topnotes.

EXAMPLE IX PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents with rich, floral, rose-like aromas andfruity undertones and hay and camphoraceous topnotes are preparedcontaining 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.50% of thehydrogenated beta damascenone mixture prepared according to Example I(bulked fractions 8-11). They are prepared by adding and homogeneouslyadmixing the appropriate quantity of hydrogenated beta damascenonemixture (bulked fractions 8-11 prepared according to Example I) in theliquid detergent. The liquid detergents are all produced using anionicdetergents containing a 50:50 mixture of sodium lauroyl sarcosinate andpotassium N-methyl lauroyl tauride. The detergents all possess apleasant fragrance with floral, rose-like, heavy fruity (berry) aromasand hay and slightly camphoraceous topnotes. When the mixture of ExampleI (bulked fractions 8-11) is replaced by the compound having thestructure: ##STR63## the detergents all possess excellent fruity, floralaromas with hay tobacco nuances. When this compound is replaced with thecompound having the structure: ##STR64## the resulting detergents havesweeter, more tobacco aromas and much deeper floral undertones.

EXAMPLE X HANDKERCHIEF PERFUME AND COLOGNE PREPARATION

The perfume composition described in Example III is incorporated incolognes at concentrations of 2.0%, 2.5%, 3.0%, 4.0% and 5.0% in 85%aqueous food grade ethanol; and into handkerchief perfumes atconcentrations of 15%, 20%, 25%, 30% and 40% (in 95% aqueous food gradeethanol). Distinctive and definitive strong otto of rose fragrances withfloral, rose-like and heavy fruity nuances and hay and slightlycamphoraceous topnotes are produced in the colognes and handkerchiefperfumes.

EXAMPLE XI HANDKERCHIEF PERFUME AND COLOGNE PREPARATION

The hydrogenated beta damascenone mixture (bulked fractions 8-11)prepared according to Example I is incorporated into colognes atconcentrations of 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5% and 4.0% in 85%aqueous food grade ethanol; and into handkerchief perfumes atconcentrations of 10%, 15%, 20% and 25% (in 95% aqueous food gradeethanol). Distinctive and definitive floral, rose-like aromas with heavyfruity (berry) undertones and hay and slightly camphoraceous topnotesare imparted to the cologne and to the handkerchief perfume. When themixture of Example I (bulked fractions 8-11) is replaced with thecompound having the structure: ##STR65## intense, fruity, floral aromasare produced in the handkerchief perfume and the cologne with haytobacco nuances. When this compound is replaced with the compound havingthe structure: ##STR66## the resulting handkerchief perfume and colognesare both sweeter and more tobacco-like with deeper floral nuances.

EXAMPLE XII PERFUMED SHAMPOO

The hair cosmetic agents shown in Table I are incorporated into a baseshampoo having the following composition:

    ______________________________________                                        Ingredients           % By Weight                                             ______________________________________                                        Ammonium lauryl sulphate                                                                            18.0                                                    Lauric isopropanolamide                                                                             1.0                                                     Texicryl 13-300 (Registered                                                                         about 1.0                                               Trademark)                                                                    Hair cosmetic agent of                                                                              1.0 to 12.0                                             Table I                                                                       Color                 0.5                                                     Water                 Balance to 100                                          ______________________________________                                    

Texicryl 13-300 (Trademark) is an aqueous emulsion of a carboxylatedacrylic copolymer available from Scott Bader & Co. Ltd.

The amount of Texicryl 13-300 (Trademark) in the shampoo is adjustedaccording to the nature of the hair cosmetic agent used so that theviscosity of the shampoo is from 500 to 2,500 cps.

The pH of the shampoo is adjusted to 6.5 or greater.

                  TABLE I                                                         ______________________________________                                        Example                     % By Weight in                                    No.       Hair Cosmetic Agent                                                                             Base Shampoo                                      ______________________________________                                         XII (A)                                                                                    Ethoxylated lanolin                                                                             2.0                                                         Glycerol monostearate                                                                           2.0                                           XII (B)       Long chain fatty condensate                                                                     5.0                                                         Glycerol monostearate                                                                           2.0                                           XII (C)       Olive oil         1.0                                           XII (D)       Olive oil         2.0                                                         Lanolin alcohol   3.0                                           XII (E)       Ethylene glycol                                                               monostearate      1.0                                                         Lanolin alcohol   4.0                                           XII (F)       Ethylene glycol                                                               monostearate      1.0                                           ______________________________________                                    

The long chain fatty condensate is an "Alcamine" resin supplied byAllied Colloids Ltd., Low Moor, Bradford, Yorks, England.

A second series of compositions is formulated by incorporating the haircosmetic agents shown in Table 2 into the above base shampoo.

In an amount of 1% (1 part by weight per 100 parts by weight ofshampoo), the hydrogenated beta damascenone (bulked fractions 8-11)produced according to Example I is added to the shampoo of each ofExamples XII (A), (B), (C), (D), (E) and (F). To each of the shampoos,an excellent floral, rose-like aroma with a heavy fruity (berry)undertone and hay and slightly camphoraceous topnotes is imparted.

When the mixture produced according to Example I is replaced with acompound having the structure: ##STR67## at a rate of 1% in the shampoo,the resultant shampoo has a fruity, floral aroma with tobaccoundertones. When this compound is replaced with 1.5% by weight of thecompound having the structure: ##STR68## the resultant shampoos in eachof Examples XII (A), (B), (C), (D), (E) and (F) have sweeter, moretobacco-like aromas with much deeper floral nuances.

EXAMPLE XIII RASPBERRY FLAVOR FORMULATION

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Vanillin              2.0                                                     Maltol                5.0                                                     Parahydroxybenzylacetone                                                                            5.0                                                     Alpha-ionone (10% in propylene glycol)                                                              2.0                                                     Ethyl butyrate        6.0                                                     Ethyl acetate         16.0                                                    Dimethyl sulfide      1.0                                                     Isobutyl acetate      13.0                                                    Acetic acid           10.0                                                    Acetaldehyde          10.0                                                    Propylene glycol      930.0                                                                         1000.0                                                  ______________________________________                                    

A mixture of compounds having the structures: ##STR69## preparedaccording to Example II is added to half of the above formulation at therate of 0.02%. The formulation with the mixture of hydrogenateddamascenones is compared with the formulation without the mixture ofhydrogenated damascenones at the rate of 0.01% (100 ppm) in water andevaluated by a bench panel.

The flavor containing the hydrogenated damascenone mixture having thestructures: ##STR70## is found to have a substantially more pleasant andbetter raspberry aroma. It is the unanimous opinion of the bench panelthat the mixture of hydrogenated derivatives of damascenone having thestructures: ##STR71## rounds the flavor out and contributes to a verynatural fresh aroma and taste as found in full, ripe raspberries.Accordingly, the addition of the mixture of hydrogenated damascenones asdescribed above is considered as substantially better than the flavorwithout said mixture of hydrogenated damascenones.

EXAMPLE XIV TOBACCO FORMULATION

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.0                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate .05                                                            Ethyl valerate .05                                                            Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above-stated tobacco flavor formulation is applied at the rate of1.0% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 150 to 250ppm. of the mixture produced according to Example II having thestructures: ##STR72## (hereinafter referred to as hydrogenateddamascenone mixture of Example II). The control cigarettes notcontaining the mixture of hydrogenated damascenone compounds producedaccording to the process of Example II and the experimental cigaretteswhich contain the mixture of hydrogenated damascenone compounds producedaccording to Example II are evaluated by paired comparison and theresults are as follows:

The experimental cigarettes are found to have more body in tobacco smokeflavor and a fuller body sensation. The tobacco-like notes are enhancedand the flavor of the tobacco on smoking is more aromatic with floral,sweet, fruity, hay, minty/spicey and woody aroma and taste nuances.

The tobacco smoke flavor of the experimental cigarettes, prior tosmoking, has sweet, fruity, hay, musty, minty/spicey, and woody notes.All cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate filter.

When the mixture of hydrogenated damascenone derivatives is added to thefilter rather than to the tobacco at either 50 ppm or 100 ppm, aninteresting and pleasant sweet, fruity aroma is obtained prior to and onsmoking the cigarettes.

EXAMPLE XV PREPARATION OF CIS DIHYDRO-DELTA-DAMASCONE ##STR73##

To a 250 ml microreaction flask equipped with magnetic stirrer,thermometer and hydrogen inlet tube is added 10 grams ofcis,trans-delta-damascone prepared according to Example I of Applicationfor U.S. Patent, Ser. No. 851,727 filed on Nov. 15, 1977 (DutchApplication 78,09271 filed on Sept. 12, 1978).

100 ml Ethyl acetate and 0.25 grams of 5% palladium-on-barium sulfateand 0.25 grams of quinoline is then added. The mixture is thenhydrogenated at atmospheric pressure at room temperature (20°-25° C.)until and uptake of 1400 ml of hydrogen is indicated. GLC analyses arerun at about every 100 ml of hydrogen uptake. The reaction is caused tocease when no more delta-damascone is present. The catalyst is filteredoff and the ethyl acetate evaporated leaving 8.5 grams of product. 150ml anhydrous diethyl ether is then added and the solution of crudeproduct is washed twice with a 4% aqueous hydrochloric acid solution (20ml) and twice with a saturated sodium chloride solution (30 ml). Theether solution is then dried over anhydrous magnesium sulfate andevaporated leaving 8.0 grams of recovered material. This material isthen distilled on a Naster-Faust spinning band column.

The resulting product has the structure: ##STR74## as confirmed by GLC,NMR and IR spectra as well as mass spectral analysis.

EXAMPLE XVI RASPBERRY FLAVOR FORMULATION

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Vanillin              2.0                                                     Maltol                5.0                                                     Parahydroxybenzylacetone                                                                            5.0                                                     Alpha-ionone (10% in propylene glycol)                                                              2.0                                                     Ethyl butyrate        6.0                                                     Ethyl acetate         16.0                                                    Dimethyl sulfide      1.0                                                     Isobutyl acetate      13.0                                                    Acetic acid           10.0                                                    Acetaldehyde          10.0                                                    Propylene glycol      930.0                                                                         1000.0                                                  ______________________________________                                    

A hydrogenated derivative of cis,trans-delta-damascone preparedaccording to Example XV having the structure: ##STR75## is added to halfof the above formulation at the rate of 0.2%. The formulation with thehydrogenated derivative of cis,trans-delta-damascone is compared withthe formulation without the hydrogenated derivative ofcis,trans-delta-damascone at the rate of 0.01% (ppm) in water andevaluated by a bench panel.

The flavor containing the hydrogenated derivative ofcis,trans-delta-damascone having the structure: ##STR76## is found tohave a substantially more pleasant and better raspberry aroma and taste.It also has the sweet, grape juice-like nuances so desired in fruitflavors. It is the unanimous opinion of the bench panel that thechemical having the structure: ##STR77## rounds the flavor out andcontributes to a very natural, fresh aroma and taste found in full, riperaspberries and, in addition, has the very interesting and useful grapejuice nuance. Accordingly, the flavor with the addition of thehydrogenated derivative of cis,trans-delta-damascone is considered assubstantially better than the flavor without said hydrogenatedderivative.

EXAMPLE XVII PREPARATION OF HYDROGENATED PRODUCT OFTRANS,TRANS-DELTA-DAMASCONE ##STR78##

To a 500 ml reaction flask equipped with thermometer, and hydrogenaddition tube and stirrer is added 50 grams oftrans,trans-delta-damascone (prepared according to Example II ofApplication for U.S. Pat. No. 851,727 filed on Nov. 15, 1977, DutchApplication 78,09271 filed on Sept. 12, 1978), 1.85 grams of a 5%palladium-on-barium sulfate catalyst, 1.0 grams quinoline and 250 mlethyl acetate. The resulting mixture is then hydrogenated (atatmospheric pressure and 20°-30° C.) until 5150 ml of hydrogen isabsorbed. Mass spectra, IR and NMR analyses yield the information thatthe product having the structure: ##STR79## is formed.

The ethyl acetate solution is then filtered to remove the catalyst andwashed with two 20 ml volumes of 4% aqueous hydrochloric acid in orderto remove the quinoline. The resulting solution is then washed withthree 20 ml volumes of saturated sodium chloride and dried on anhydrousmagnesium sulfate. After evaporation, 47.5 grams of crude productresults which is distilled to yield 11 fractions. FIG. 19 is the NMRspectrum for the compound having the structure: ##STR80##

EXAMPLE XVIII

Utilizing the procedure of Example I of column 15 of U.S. Pat. No.3,632,396, a nonwoven cloth substrate useful as a dryer-addedfabric-softening article of manufacture is prepared wherein thesubstrate, the substrate coating and the outer coating and the perfumingmaterial are as follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57 percent C₂₀₋₂₂ HAPS

22 percent isopropyl alcohol

20 percent antistatic agent

1 percent of at least one butenoyl and/or butanoyl cyclohexane orcyclohexene compound or mixture thereof of our invention as set forth inthe Table I below and giving rise to the aroma nuances as set forth insaid Table I below:

                  TABLE I                                                         ______________________________________                                        DESCRIPTION OF PERFUME                                                                           FRAGRANCE                                                  INGREDIENT         CHARACTERISTICS                                            ______________________________________                                         ##STR81##         At 1% in dipropylene glycol, a sweet, dry, fruity,                            floral aroma with hay tobacco nuances.                      ##STR82##         A floral (rose) fruity (prune, berry-like) aroma.           ##STR83##         A burnt, rosey aroma with weak floral nuances.              ##STR84##         A floral, rose-like aroma with heavy fruity (berry)                           undertones; also hay and slightly camphoraceous                               nuances.                                                    ##STR85##                                                                     ##STR86##                                                                     ##STR87##                                                                     ##STR88##                                                                    (Mixture)                                                                     ______________________________________                                    

Fabric-softening compositions prepared as set forth above having theabove aroma characteristics essentially consist of a substrate having aweight of about 3 grams per 100 square inches, a substrate coating ofabout 1.85 grams per 100 square inches of substrate and an outer coatingof about 1.4 grams per 100 square inches of substrate, thereby providinga total aromatized substrate and outer coating weight ratio of about 1:1by weight of the substrate. The aromas as set forth in Table I above areimparted in a pleasant manner to the head space in the dryer onoperation thereof using the said dryer added fabric softening nonwovenfabric.

What is claimed is:
 1. The compound having the structure selected fromthe group consisting of: ##STR89##
 2. A mixture of compounds having thestructures: ##STR90##
 3. The compound defined by the structure:##STR91##
 4. A mixture of compounds having the structures: ##STR92##